High molecular weight polyols, process for preparation and use thereof

ABSTRACT

The invention is a high molecular weight polyether polyol prepared by the reaction of one or more compounds having one or more active hydrogen compounds with one or more alkylene oxides in the presence of a catalyst comprising calcium having counterions of carbonate and a C 6-10  alkanoate in a solvent or dispersant which does not contain active hydrogen atoms. The polyether polyol prepared preferably has an equivalent weight of from about 1000 to about 20,000, a polydispersity of 1.3 or less and a residual catalyst level of from about 0 to about 2000 parts per million (ppm). In another embodiment the invention is a process for preparing such high molecular weight polyether polyols. The process comprises first, contacting one or more compounds having one or more active hydrogen atoms with one or more alkylene oxides in the presence of a catalyst. The catalyst comprises calcium having counterions of carbonate and a C 6-10  alkanoate in a solvent, wherein the solvent does not contain active hydrogen atoms. The mixture is exposed to conditions at which the alkylene oxides react with the compound containing more than one active hydrogen atoms such that a polyether polyol is prepared which has an equivalent weight of from about 1,000 to about 20,000, a polydispersity of about 1.3 or less and a residual catalyst level of from about 0 to about 1000 (ppm).

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of application Ser. No. 09/300,232,filed Apr. 27, 1999, which also claims priority from U.S. ProvisionalApplication No. 60/083,126 filed on Apr. 27, 1998.

BACKGROUND OF THE INVENTION

This patent application relates to novel high molecular weight alkyleneoxide based polyether polyols and a process for their preparation. Thisapplication further relates to the use of such high molecular weightalkylene oxide based polyether polyols to prepare prepolymers useful inhigh performance adhesives and elastomers. This invention furtherrelates to high viscosity polyether polyols useful as lubricants. Theinvention further relates to high molecular weight polyether polyolsuseful as thickening agents in hydraulic fluids.

Polyether polyols used in preparing polyurethane adhesives andelastomers are usually prepared by reacting an initiator compound havinga plurality of active hydrogen atoms with an alkylene oxide in thepresence of basic catalysts such as tertiary amines, sodium andpotassium hydroxides and sodium where a sodium derivative such as thealkylate of alkoxide is formed in situ. However, these catalysts mustusually be removed by filtration and/or neutralization or other catalystremoval methods prior to use, particularly when prepolymers are to beprepared from such polyether polyols.

Olstowski and Nafziger, U.S. Pat. No. 4,282,387, issued Aug. 4, 1981,incorporated herein by reference, disclosed preparing polyols byreacting alkylene oxides with hydroxyl initiator compounds in thepresence of catalysts of calcium, strontium, or barium salts of organicacids. These catalysts do not need to be removed before the resultantproduct is used in the preparation of polyurethanes. Such catalysts aregenerally available in a mineral spirit solvent which further containsmonoether glycols. Such monoether glycols contain active hydrogen atomsand act as initiators. This results in the preparation of a mixture ofpolyols wherein some of the polyols are mono functional with respect tothe hydroxyl group. The presence of mono functional polyether polyolsdecrease the physical properties of the elastomers that are made fromthem. They also form polyether polyols which have low molecular weightspecies and result in a high polydispersity. Polydispersity is definedas the weight average molecular weight divided by the number averagemolecular weight. A high polydispersity indicates that the polyetherpolyol prepared is a mixture of polyether polyols having a wide range ofmolecular weights. A high polydispersity and low molecular weightrenders such polyether polyols unsuitable for high performanceapplications such as high performance elastomers and adhesives. Many ofthe polyether polyols prepared using such a catalyst system areinitiated with a monofunctional glycol ether and are monofunctional, andtherefore are not useful in high performance applications.

Yates et al. U.S. Pat. No. 4,326,047 discloses a process for preparingpolyols using the catalysts described in Olstowski, wherein the catalystis precipitated from the mineral spirits carrier and the glycol ethercoupling agent. The resulting catalyst is solid. To be effective thiscatalyst must be redissolved in the reaction medium. This extra steptakes time and negatively affects the productivity of the reaction andthe polydispersity of the product prepared.

Hydraulic fluids are generally thicken ed with polyether polyols. Inorder to achieve the desired viscosity of such hydraulic fluids, it isoften necessary to use a high concentration of polyether polyols in thewater based hydraulic fluids. A common hydraulic fluid is ISO VG 46hydraulic fluid which has a viscosity of 46 centistokes at 40° C. Mostpolyether polyols used in this application have a relatively lowmolecular weight. In order to prepare a hydraulic fluid meeting thisrequirement with these low molecular weight polyethers a concentrationof from about 30 to about 70 percent by weight of polyether polyol isrequired. This formulation is expensive due to the need for such a highconcentration of polyether polyols. There are known high molecularweight polyethylene oxide based polyethers used as thickening agents inhydraulic fluid available from Union Carbide under the tradename POLYOXWSRN-10™. These generally have a molecular weight of 100,000 or greater.These can be used at a low concentration but exhibit poor shearstability and the fluid containing these polyethers is not shear stableand suffers from a reduction in viscosity during use. It would bedesirable to have a high molecular weight polyether polyol which couldthicken hydraulic fluid to the desired level at a significantly lowerconcentration and which is shear stable.

Some lubricants are designed to have a certain viscosities at 40° C.,ISO VG 1000 lubricants demonstrate a viscosity of 1000 centistokes at40° C. ISO VG 2000 lubricants demonstrate a viscosity of 2000centistokes at 40° C. Polyether polyols made with basic catalystsgenerally do not have sufficient molecular weight to achieve the desiredviscosities. High molecular weight polyether polyols which havesufficient viscosity to function as these lubricants are desired.

What is needed are high molecular weight polyether polyols which areuseful in high performance applications. What is further needed is aprocess for the preparation of such high performance polyether polyols.What is also needed is a prepolymer useful in preparing high performanceelastomers and adhesives prepared from such high molecular weightpolyether polyols. What is further needed are high molecular weightpolyether polyols which can be used as a thickener in water basedhydraulic fluids and which are shear stable under lubricatingconditions. What is needed is a high viscosity polyether polyol whichcan achieve the desired ISO VG 1000 and ISO VG 2000 viscosities.

SUMMARY OF THE INVENTION

The invention is a high molecular weight polyether polyol prepared bythe reaction of one or more compounds having one or more active hydrogencompounds with one or more alkylene oxides in the presence of a catalystcomprising calcium having counterions of carbonate and a C₆₋₁₀ alkanoatein a solvent or dispersant which does not contain active hydrogen atoms.The polyether polyol prepared preferably has an equivalent weight offrom about 1000 to about 20,000, a polydispersity of about 1.30 or less,and preferably of about 1.2 or less and a residual catalyst level offrom about 0 to about 2000 parts per million (ppm).

In another embodiment the invention is a process for preparing such highmolecular weight polyether polyols. The process comprises first,contacting one or more compounds having one or more active hydrogenatoms with one or more alkylene oxides in the presence of a catalyst.The catalyst comprises calcium having counterions of carbonate and aC₆₋₁₀ alkanoate in a solvent, wherein the solvent does not containactive hydrogen atoms. The mixture is exposed to conditions at which thealkylene oxides react with the compound containing more than one activehydrogen atoms such that a polyether polyol is prepared which has anequivalent weight of from about 1,000 to about 20,000, a polydispersityof about 1.2 or less and a residual catalyst level of from more thanabout 0 to about 2000 (ppm).

In another embodiment, the invention is a hydraulic fluid comprisingfrom about 1 to about 50 percent by weight of a polyether polyol asdescribed above and from about 50 to about 99 percent by weight ofwater. Such polyether polyols allow the preparation of hydraulic fluidshaving the required viscosities with a lower concentration of polyetherpolyols incorporated into such hydraulic fluids than heretofore has beenpossible. Such polyether polyols are shear stable under conditions ofuse.

In yet another embodiment the invention is a lubricant compositioncomprising a polyether polyol as described hereinbefore.

In yet another embodiment the invention is a prepolymer comprising thereaction product of a polyether polyol as described before with anisocyanato silane having at least one silane moiety which has bondedthereto a hydrolyzable moiety.

The invention in another embodiment is a process for the preparation ofa silyl terminated prepolymer. The process comprises contacting apolyether polyol as described herein with an isocyanato silane having atleast one silane moiety which has bonded thereto a hydrolyzable moiety.The polyether polyol and isocyanato silane react under conditions suchthat the hydroxy moieties of the polyol react with isocyanate moietiesof the silane so as to place a terminal silane moiety on the polyetherpolyol. The process is performed preferably without the addition ofcatalyst.

The process of the invention allows the preparation of high molecularweight polyether polyols which have a low polydispersity. The polyetherpolyols are useful in preparing polyurethane and reactive siliconefunctional prepolymers which are stable under ambient conditions. Suchprepolymers are useful in preparing elastomers, sealants and adhesives.

BRIEF DESCRIPTION OF FIGURE

FIG. 1 illustrates the Gel Permeation Chromatography curves of twopolyols, one polyol according to the invention and a second madeaccording to the closest prior art.

DETAILED DESCRIPTION OF INVENTION

The polyether polyols of the invention are generally prepared byreacting an initiator, a compound having one or more active hydrogenatoms, with an alkylene oxide in the presence of a suitable catalystunder appropriate conditions for the alkylene oxide to react with theactive hydrogen moiety of the initiator so as to add a series of etherunits to the initiators thereby preparing a polyether polyol. Initiatorswhich are useful in this invention are well known to those skilled inthe art. Preferable initiator compounds which are employed to preparethe polyether polyols are compounds having about 1 to about 8,preferably about 2 to about 8, more preferably about 2 to about 4, mostpreferably about 2 to about 3 active hydrogens. Preferable initiatorcompounds include, for example, alcohols, glycols, low molecular weightpolyols, glycerin, trimethylol propane, pentaerythritol, glucosides,sugars, ethylene diamine, diethylene triamine, and the like.Particularly suitable glycols include ethylene glycol, 1,2-propyleneglycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol,1,4-butylene glycol, 1,2-pentylene glycol, 1,3-pentylene glycol,1,4-pentylene glycol, 1,5-pentylene glycol, neopentyl glycol and varioushexane diols, mixtures thereof and the like.

Alkylene oxides useful in this invention are well known to those skilledin the art and are disclosed in U.S. Pat. No. 4,326,047 and U.S. Pat.No. 4,282,387 relevant portions incorporated herein by reference.Preferred alkylene oxides include ethylene oxide, propylene oxide,1,2-butylene oxide 2,3-butylene oxide, or hexene oxide. The mostpreferred alkylene oxides are ethylene oxide and propylene oxide withpropylene oxide most preferred. Combinations of the above mentionedalkylene oxides may be used in random or block polymers.

The catalysts used in preparing the polyether polyols of this inventionare calcium catalysts which contain both carbonate and C₆₋₁₀ alkanoatecounterions and preferably C₈ counterions. The catalyst is dispersed ordissolved in a dispersant or solvent which has no active hydrogen atomscapable of initiating a polyether. Preferably, the solvent or dispersantis a hydrocarbon or mixture of hydrocarbons and is soluble ordispersible in the polyether polyol and the components used to preparethe polyether polyol. In a more preferred embodiment, the solvent ordispersant is mineral spirits. Preferably the alkanoate counterions areC₆₋₁₀, and more preferably C₈ residues of organic acids. In a preferredembodiment the alkanoates are derived from substantially pure organiccarboxylic acids. Preferably the pure carboxylic acids are synthetic, assynthetic carboxylic acids generally exhibit higher purities. Thecarbonate counterions result from contacting calcium and the organiccarboxylic acid with carbon dioxide. The ratio of calcium ions toorganic acid ions is from about 1:0.2 to about 1:1. Preferably the ratiois from about 1:0.3 and about 1:0.7. The catalysts may be prepared bycontacting the appropriate ratio of calcium hydroxide with a C₆₋₁₀carboxylic acid and bubbling carbon dioxide through the mixture to formcarbonate moieties. The use of a solvent without active hydrogen atomsprevents the unwanted initiation of polyols with an undesired initator.The use of substantially pure organic acids is believed to enhance thepolydispersity and performance of the resulting polyols in theapplications described herein

In the preparation of the polyether polyols of the invention, theinitiator alkylene oxides and catalyst in an appropriate solvent arecontacted. Typically such contacting takes place in the absence ofoxygen and atmospheric moisture. Preferably, the contacting takes placeunder an inert atmosphere, such as nitrogen or argon. The ratio ofinitiator to alkylene oxide is chosen to achieve the desired molecularweight or equivalent weight of the polyether polyol. This ratio can bereadily calculated by one skilled in the art. The amount of catalystused should be sufficient such that the residual catalyst remaining inthe polyether polyol upon completion of the reaction is above 0 ppm morepreferably 200 ppm or greater and most preferably 300 part per millionor greater. Preferably the amount of catalyst used is chosen such thatthe amount of catalyst left in the polyether polyol upon completion ofthe reaction is about 2000 ppm or less and more preferably about 1000ppm or less. In the embodiment wherein the polyether polyol is used toprepare elastomers, the resulting high molecular weight polyether polyolpreferably contains a residual catalyst amount of about 200 ppm orgreater, more preferably about 300 ppm or greater and most preferablyabout 400 ppm or greater. Preferably the residual catalyst level isabout 1000 ppm or less more preferably about 800 ppm or less, even morepreferably about 600 ppm or less, and most preferably about 500 ppm orless. In some embodiments where the polyether polyol is used to prepareelastomers it may be desirable to remove all of the residual catalyst.In the embodiment wherein the polyether polyol is used in a hydraulicfluid or a lubricant the resulting high molecular weight polyetherpolyol contains a residual catalyst amount of about 200 ppm or greater,more preferably about 300 ppm or greater and most preferably about 400ppm or greater. Preferably the residual catalyst level is about 2000 ppmor less, more preferably about 1000 ppm or less, even more preferablyabout 800 ppm or less, and most preferably about 600 ppm or less.

In some embodiments it may be desirable to remove the residual catalystfrom the polyether polyols of the invention. This can be achieved bycontacting the polyether polyol of the invention with magnesium silicateor phosphoric acid and filtering the polyol with diatomaceous earth. Thecomplex of the calcium catalyst and the additives are removed on thefilter material. In those embodiments where the calcium is removed theresulting parts per million of the catalyst remaining in the polyol canbe 0.

The reactants are reacted preferably at a temperature or about 90° C. orgreater, more preferably about 100° C. or greater and most preferablyabout 110° C. or greater. The reactants are reacted preferably at atemperature of about 150° C. or less, more preferably about 130° C. orless and most preferably about 120° C. or less. The reactants arecontacted for a time sufficient to prepare the desired high molecularweight polyether polyol. The reaction time is controlled by the feedrate, reactor size, catalyst concentration and temperature. One skilledin the art can determine the appropriate time based on these variables.The unreacted alkylene oxides and any solvents may be removed from thereaction by stripping them off using means well known to those skilledin the art.

In the embodiment wherein the polyether polyol is used to prepareelastomers, the polyether polyol preferably has an weight averagemolecular weight of about 2,000 or greater, more preferably about 3,000or greater, even more preferably about 6,000 or greater and mostpreferably about 10,000 or greater. The resulting polyether polyolpreferably has a weight average molecular weight of about 20,000 orless, more preferably about 16,000 or less and most preferably about14,000 or less. In the embodiment wherein the polyether polyol is usedin a hydraulic fluid the polyether polyol preferably has a weightaverage molecular weight of about 20,000 or greater, more preferablyabout 25,000 or greater, and most preferably about 30,000 or greater.The resulting polyol preferably has a molecular weight of about 80,000or less, more preferably about 60,000 or less and most preferably about50,000 or less. In the embodiment wherein the polyether polyol is usedas a lubricant the polyether polyol preferably has a weight averagemolecular weight of about 1,000 or greater, more preferably about 2,000or greater, most preferably about 5,000 or greater. The resulting polyolpreferably has a weight average molecular weight of about 20,000 orless, more preferably about 16,000 or less and even more preferablyabout 12,000 or less and most preferably about 10,000 or less. Theresulting polyether polyol preferably has a polydispersity of about 1.20or less and more preferably about 1.12 or less.

Preferably the polyether polyol of the invention corresponds to Formula1:

R¹—((CH(R²)CH(R²)O)_(m)—H)_(p)  (1)

wherein:

R¹ is the residue of a compound having from about 1 to about 8 activehydrogen atoms;

R² is independently in each occurrence hydrogen or a C₁₋₆ saturated orunsaturated hydrocarbon chain;

m is independently in each occurrence a number such that the equivalentweight of the polyether polyol is from about 1,000 to about 20,000; and,

p is independently in each occurrence from about 1 to 8.

Preferably R¹ is a C₁₋₈ alkyl or cycloalkyl moiety or oxygen. Morepreferably, R¹ is a C₂₋₄ alkyl group or oxygen. R² is preferablyhydrogen, methyl or ethyl and most preferably hydrogen or methyl. In theembodiment where the polyether polyol is used to prepare an elastomericcomposition, m is independently in each occurrence a number such thatthe equivalent weight of the polyol is from about 1,000 to about 20,000and more preferably from about 5,000 to about 8,000. In the embodimentwhere the polyether polyol is used to prepare a hydraulic fluid, m isindependently in each occurrence a number such that the equivalentweight of the polyol is from about 10,000 to about 30,000, and morepreferably from about 10,000 to about 20,000. In the embodiment wherethe polyether polyol is used as a lubricant, m is independently in eachoccurrence a number such that the equivalent weight of the polyol isfrom about 2,000 to about 7,000, and more preferably from about 3,000 toabout 5,000 more preferably from about 3,000 to about 4,000. P ispreferably 4 or less and more preferably 3 or less. In the embodimentwhere R¹ is oxygen p must be 2.

The polyether polyols of the invention also demonstrate a lowunsaturation level, preferably about 0.04 milliequivalents ofunsaturation per gram of polyol or less and more preferably about 0.02milliequivalents of unsaturation per gram of polyol or less.

The high molecular weight polyether polyols of this invention can beused to prepare reactive silicone functional prepolymers. Suchprepolymers are prepared by reacting a high molecular weight polyetherpolyol of this invention with an isocyanato silane. Such isocyanatosilane requires a silane group with a hydrolyzable moiety attachedthereto. The isocyanato moiety of the isocyanato silane reacts with theactive hydrogen atoms of the polyether polyol to place the reactivesilicone containing moiety onto the polyol. Isocyanato silanes useful inthe invention are described in U.S. Pat. No. 4,618,656 at column 3,lines 24 to 34 incorporated herein by reference. Preferably suchisocyanato silanes correspond to the following formula.

wherein:

R³ is independently in each occurrence a hydrolyzable moiety;

R⁴ is independently in each occurrence hydrogen or an hydrocarbylmoiety;

a is independentely in each occurrence an integer of from 0 to 2;

Z is independently in each occurrence a C₁₋₄₀ divalent hydrocarbylmoiety.

In the above mentioned formula Z is preferably a C₁₋₂₀ divalenthydrocarbyl moiety, more preferably C₁₋₈ alkylene and most preferablyC₁₋₃ alkylene. R³ is preferably a hydrogen atom, a halogen atom, analkoxy group, an acyloxy group, a ketoximate group, an amino group, anamide group, an acid amide group, an amino-oxy group, a mercapto groupor an alkenyloxy group. Among them, a hydrogen atom, an alkoxy group, anacyloxy group, a ketoximate group, an amino group, an amide group, anamino-oxy group, a mercapto group, or an alkenyloxy group are preferred.In particular, an alkoxy group, e.g., a methoxy group or ethoxy, ispreferred because of its mild hydrolyzability and ease in handling. Thereaction of an isocyanato silane with a polyol is well known to thoseskilled in the art.

The process for the preparation of a silyl terminated prepolymercomprises contacting a polyether polyol with an isocyanato silane havingat least one silane moiety which has bonded thereto a hydrolyzablemoiety under conditions such that the hydroxy moieties of the polyolreact with isocyanate moieties of the silane so as to place a terminalsilane moiety on the polyether polyol wherein the contacting isperformed without the addition of catalyst. The reaction of thepolyether polyol with an organo functional silane can be performed usingconventional processes such as those disclosed in U.S. Pat. No.4,625,012 incorporated herein by reference. The polyether polyols of theinvention allow the preparation of silane terminated polyethers by thereaction of isocyanato silanes with the polyether polyols of theinvention without the addition of additional catalysts. The residualcalcium catalysts from the polyether polyol formation reaction sequenceis sufficient to catalyze the reaction. After the reaction is completethe residual calcium catalyst can be neutralized with acid. If desired,a standard polyurethane catalyst such as those disclosed in U.S. Pat.No. 4,625,012 at column 5, lines 14 to 23 may be added. It isdisadvantageous to add such catalysts as this may impact the stabilityof the prepolymer prepared negatively. It has been discovered that theprepolymer, if prepared in the absence of standard polyurethanecatalysts, is stable to condensation if exposed to atmospheric moisture.Such a prepolymer can be used to prepare elastomers and adhesivecompositions. Such elastomeric materials in adhesive compositionsdemonstrate better stability and elastomeric properties if prepared inthe absence of additional polyurethane catalysts. The reaction of theisocyanato silane with a polyol preferably takes place at a temperatureof about 0° C. or greater and more preferably about 25° C. or greater.The reaction preferably takes place at a temperature of about 150° C. orless and more preferably at about 80° C. or less. This reactionpreferably is performed in an inert atmosphere such as under a nitrogenblanket. The reaction is allowed to proceed until the desired silanefunctionality is achieved. In a preferred embodiment a sufficient amountof isocyanato silane is used to react with all of the hydroxylfunctionality contained in the polyol. In one embodiment a polyurethaneprepolymer can be prepared from the polyether polyols of the invention.These prepolymers are prepared by the reaction of the polyethers polyolswith a polyisocyanate (having 2 or more isocyanate moieties permolecule). This reaction is well known in the art. See Hsieh U.S. Pat.No. 5,852,137 incorporated herein by reference. A prepolymer havingisocyanate functionality is prepared when there are excess isocyanateequivalents in the reaction as compared to active hydrogen containingmoieties. The prepolymer will be hydroxyl functional if excess polyol isused as compared to isocyanate.

The prepolymer may be prepared by any suitable method, such as bulkpolymerization and solution polymerization. The reaction to prepare theprepolymer is carried out under anhydrous conditions, preferably underan inert atmosphere such as a nitrogen blanket, to prevent cross-linkingof the isocyanate groups by atmospheric moisture. The reaction ispreferably carried out at a temperature or about 0° C. or more and morepreferably about 25° C. or greater. The reaction is preferably carriedout at a temperature of about 150° C. or less and more preferably about80° C. or less. The reaction is allowed to proceed until the residualisocyanate content determined by titration of a sample is very close tothe desired theoretical value. The reaction to prepare the prepolymermay be carried out in the presence of urethane catalysts. Examples ofsuch include the stannous salts of carboxylic acids, such as stannousoctoate, stannous oleate, stannous acetate, and stannous laurate. Also,dialkyltin dicarboxylates such as dibutyltin dilaurate and dibutyltindiacetate are known in the art as urethane catalysts, as are tertiaryamines and tin mercaptides. Preferably, the reaction to prepare theprepolymer is catalyzed by stannous octoate. The amount of catalystemployed is generally between about 0.005 and about 5 percent by weightof the mixture catalyzed, depending on the nature of the isocyanate. Ina preferred embodiment the residual catalyst from the polyol synthesisreaction is sufficient to catalyze the preparation of the prepolymerwithout the addition of another polyurethane catalyst.

The polyurethane prepolymers can be used in adhesive compostions such asdisclosed in Risk U.S. Pat. No. 4,758,648; Bhat U.S. Pat. No. 5,603,798;and Hsieh U.S. Pat. No.5,852,137 incorporated herein by reference.Adhesive compositions containing polyurethane prepolymers prepared asdescribed herein without the addition of a polyurethane catalystdemonstrate enhanced stability as compared to formulations where theprepolymer is prepared using a standard polyurethane catalyst.

In addition these polyurethane prepolymers form elastomers when cured byknown curing agents or cross-linkers. The cross-linkers utilized in thisinvention include any cross-linker which is known and which preferablyhas an equivalent weight of about 200 or less. Cross-linkers as usedherein refers to compounds which are also commonly referred to as chainextenders. Such cross-linkers are low molecular weight compounds havingtwo active hydrogen atoms which react with isocyanate moieties.Preferred cross-linkers are C₃-C₁₀ alkylene diols, C₃-C₁₀ cycloalkylenediols, hydroquinone di(beta-hydroxyl ethyl)ether, ethoxylated bisphenolA, 4,4′-methylene bis(2-chloroaniline),4,4′-methylenebis(3-chloro-2,6-diethylaniline),3,5-dimethylthio-2,4-toluenediamine,3,5-dimethylthio-2,6-toluenediamine, trimethylene glycoldi-p-aminobenzoate and 1,4-bis(β-hydroxyethoxy)benzene. Examples ofC₃-C₁₀ alkylene diols are 1,3-propanediol, 1,4-butanediol,1,6-hexanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanedioland 2-butyl-2-ethyl-1,3-propanediol. The cross-linking agents arepresent preferably in an amount of about 1 percent by weight or greaterand more preferably about 5 percent by weight or greater based on thetotal weight of the formulation. Preferably, the cross-linking agent ispresent in an amount of about 30 percent by weight or less based on thetotal weight of the total formulation, and more preferably about 15percent or less. The elastomers may be prepared in the presence ofstandard polyurethane catalysts. In addition, standard elastomericadditives may be present such as fillers and antioxidants. Theelastomers may be formed at temperatures of about 15° C. or greater,more preferably about 20° C. or greater and most preferably about 25° C.or greater. Preferably, the elastomers are formed at a temperature ofabout 100° C. or less, more preferably about 40° C. or less. Afterformation the elastomers may be subjected to curing conditions. Suchcuring conditions include curing at about 80° C. or greater for about 1hour or greater and may be subjected to post-curing at about 80° C. orgreater and preferably about 100° C. or greater for about 12 hours orgreater and preferably about 24 hours or greater.

In another embodiment of the invention the polyether polyols of theinvention may be used as thickeners in water based hydraulic fluids. Insuch embodiments the alkylene oxides used to prepare the polyetherpolyols, are preferably ethylene oxide and propylene oxide and theinitiator is preferably a di or tri functional initiator, morepreferably a tri functional initiator. In a preferred embodiment thepolyether polyol is a mixture of ethylene oxide and propylene oxideunits in either block or random form. Preferably the ethylene oxideunits are about 95 percent by weight or less of the polyether polyol andmore preferably about 75 percent by weight or less of the polyetherpolyol. A sufficient amount of the polyether polyol is used to achievethe desired viscosity of the fluid. One standard lubricant grade is ISOVG 46 hydraulic fluid, which has a viscosity of 46 centistokes at 40° C.The polyether polyols of the invention exhibit the appropriate viscosityat less than about 30 percent by weight of polyether polyol in theformulation. Preferably, the formulation contains about 5 percent byweight or greater of polyol of the invention, more preferably about 10percent by weight or greater of the polyether polyol and most preferablyabout 14 percent by weight or greater of polyether polyol. Preferably,the formulation has about 30 percent by weight or less of the polyetherpolyol, more preferably about 29 percent by weight or less of polyetherpolyol, even more preferably about 20 percent by weight or less and mostpreferably about 16 percent by weight or less. Preferably, theformulation contains about 70 percent by weight or greater of water,more preferably about 71 percent by weight or greater of water, morepreferably about 80 percent by weight or greater of water and mostpreferably about 84 percent by weight or greater of water. Preferablythe formulation has about 95 percent by weight or less of water, morepreferably about 90 percent by weight or less of water and mostpreferably about 86 percent by weight or less of water. At higherethylene oxide contents in the polyether polyol, the polyether polyolcan phase separate from water at high temperatures. Under certaincircumstances the polyether polyol will phase separate from the waterbase of the hydraulic fluid. In this embodiment the polyether polyolpreferably has a ethylene oxide content of about 75 percent by weight orgreater and more preferably a polyethylene oxide content of about 90percent by weight or less and most preferably about 80 percent by weightor less. This phase separation preferably occurs at a temperature ofabout 50° C. or greater and most preferably at about 70° C. or greaterand preferably at about 80° C. or less. This phase separation from thebase fluid allows for easy recovery of the polyether polyol from usedhydraulic fluid and is more environmentally friendly. The hydraulicfluids of the invention are more shear stable and the polyether polyolsof the invention dissolve into the water solution easier thanconventional polyols, i.e. the POLYOX polyethylene oxide based polyols.

Hydraulic fluids of the invention can further contain other componentswell known to those skilled in the art. Additives used in such hydraulicfluids are disclosed in U.S. Pat. No. 4,481,125, U.S. Pat. No.4,312,768, U.S. Pat. No. 4,093,554, U.S. Pat. No. 4,391,722, U.S. Pat.No. 4,686,058, U.S. Pat. No. 5,326,485 and U.S. Pat. No. 4,702,854,(relevant portions incorporated herein by reference).

In one embodiment certain polyether polyols of the invention may be usedas lubricants. In this embodiment the polyether polyol comprises thebulk of the lubricant. Common additives known to one skilled in the artmay be mixed with the polyether polyol to prepare the lubricant.

The final lubricant or hydraulic fluid compositions of these embodimentsmay contain effective amounts of ashless additives, such asantioxidants, corrosion inhibitors, metal deactivators, lubricityadditives, extreme pressure additives and viscosity modifiers as may berequired. The polyether polyols used as lubricants are prepared asdescribed before with the viscosity being monitored until the targetviscosity is achieved. Lubricants having a viscosity of 1000 centistokesand 2000 centistokes at 40° C. can be prepared from the polyetherpolyols of the invention as described.

Examples of useful ashless antioxidants which can be used herein arephenyl naphthylamines, i.e., both alpha and beta-naphthyl amines;diphenyl amine; iminodibenzyl; p,p-dibutyl-diphenylamine;p,p-dioctyldiphenylamine; and mixtures thereof. Other suitableantioxidants are hindered phenolics such as 2-t-butylphenol,2,6-di-t-butylphenol and 4-methyl-2,6-di-t-butylphenol and the like.

Examples of suitable ashless metal corrosion inhibitors are commerciallyavailable, such as IRGALUBE 349™ from Ciba-Geigy. This inhibitorcompound is an aliphatic amine salt of phosphoric acid monohexyl ester.Other useful metal corrosion inhibitors are NA-SUL DTA™ and NA-SUL EDS™from the King Industries, Inc. (dinonylnapthalene sulfonate,diethylenetriamine dinonylnapthalene sulfonate and ethylene diaminedinonylnapthalene sulfonate)and Sarcosyl O,N-methyl oelosarcosine, fromCiba, Inc.

Examples of suitable ashless cuprous metal deactivators are imidazole,benzimidazole, pyrazole, benzotriazole, tolutriazole, 2-methylbenzimidazole, 3,5-dimethyl pyrazole, and methylene bis-benzotriazole.

Examples of suitable viscosity modifiers are pentaeryritoltetrapelargonate and trimethyolpropane triheptonate.

An effective amount of the foregoing additives for use in a lubricant ora hydraulic fluid is generally in the range from about 0.1 to about 5.0percent by weight for antioxidants, about 0.1 to about 5.0 percent byweight for the corrosion inhibitors, and about 0.001 to about 0.5percent by weight for the metal deactivators. The foregoing weightpercentages are based on the total weight of the polyether polyols. Itis to be understood that more or less of the additives may be useddepending upon the circumstance for which the final composition is to beused.

Unless otherwise stated all molecular weights as used herein aredetermined by titrating to determine the hydroxyl number and calculatingthe molecular weight according to the formula. If the molecular weightis designated as a number average molecular weight it is determinedaccording to gel permeation chromatography.

Specific Embodiments

The following examples are included for illustrative purposes only andare not intended to limit the scope of the invention. Unless otherwisestated all parts and percentages are based on weight.

EXAMPLE 1 Preparation of a High Molecular Weight Polyether Diol

A mixture of 97.3 grams of polyglycol P1000, a 1000 MW polypropyleneoxide diol from which essentially all of the catalyst (KOH) had beenremoved, and 9.73 grams of 10 percent calcium, CEM ALL D10™ (about 50percent by weight calcium isooctoate in mineral spirits carrier, andwhich contains no glycol ether stabilizers, available from OMG Americas,Cleveland, Ohio) was placed in a dry, steam heated and stirred pressurereactor which was then purged with nitrogen several times. The mixturewas heated to 100° C. and 1,985 grams of propylene oxide was added withrapid stirring. The product was a liquid having an equivalent weight of5,218 determined by a wet method for hydroxyl analysis. The numberaverage molecular weight of the product was 9,978 as determined by gelpermeation chromatography using polyglycol standards and apolydispersity of 1.1 determined by size exclusion chromatography.

EXAMPLE 2 Preparation of a High Molecular Weight Isocyanate Prepolymer

300.35 grams of the polyglycol of Example 1 was mixed with 600 grams oftoluene and stirred at 23° C. until well mixed. 8.2 milliliters oftoluene diisocyanate were added and heated to 100° C. with stirring.After two hours the toluene was removed with vacuum. 308 grams of aclear viscous light yellow liquid were recovered. The IR spectrum of theproduct isocyanate peak at 2274 CM-1 was greatly reduced and theurethane peak at 1650 CM-1 increased indicating that most of theisocyanate had reacted. This NCO concentration of this mixture was 0.69percent measured by a wet chemical method.

EXAMPLE 3 Preparation of a High Molecular Weight Urethane Elastomer

1.7 grams dibutyl tin dilaurate (CATACHK 820™ from Ferro Chemical Corp.)were added to 170 grams of the product of example 2. The mixture wasmixed well. A 30 milliliter film was cast on glass plates and allowed tocure overnight at 23° C. The film demonstrated good adhesion to theglass plates. The elastomer was cured in a 70 percent relative humiditychamber for 4 days. The average physical properties of the elastomer (5replicates) were 301 psi tensile strength, modulus 11.44 psi, 0.64pounds load at tear and a 934 percent elongation at break.

EXAMPLE 4 Preparation of High Molecular Weight Silyl TerminatedPolyether

In a dried, heated, nitrogen purged and mechanically stirred 500milliliter round bottom flask was added 134.94 grams of the product ofExample 1, 6.33 grams of Siliquest A1310,gamma-isocyanatopropyltriethoxysilane, and 1.52 grams dibutyltindilaureate. The mixture was heated to 100° C. with stirring andimmediately allowed to cool to room temperature. A 30 milliliter filmwas drawn on glass plates. The film was allowed to moisture cureovernight. The film was tack free in about 24 hours. The film was placedin a 70 percent humidity chamber for 5 days and then placed in an ovenat 50° C. overnight. The cured film had a 73 psi tensile strength, 35psi modulus, and a 347 percent elongation at break.

EXAMPLE 5 Preparation of an ISO VG 1000 Lubricant

A mixture of 792 grams of polyglycol PB200, a 910 molecular weightpolypropylene oxide monol initiated with n-butanol, from whichessentially all of the catalyst (KOH) had been removed, and 25.3 gramsof 10 percent Calcium CEM ALL D10™ was placed in a dry steam heated andstirred pressure reactor which was then purged with nitrogen severaltimes. The mixture was heated to 100° C. and 5,230 grams of propyleneoxide was added with rapid stirring. The product was a liquid having anequivalent weight of 4,968 determined by a wet method for hydroxylanalysis. The number average molecular weight of the product was 5,000.The polydispersity was 1.26 as determined by size exclusionchromatography. The 100° F. viscosity was 1,182 cS and the 210° C.viscosity was 162.2 cS. The calculated 40° C. viscosity was 1182 cS.This is an ISO viscosity grade of 1000.

EXAMPLE 6 Preparation of a Water Soluble High Molecular Weight PolyetherTriol

A 2 gallon reactor was charged with 92 grams glycerin (1 mole) and 250grams 10 percent Calcium CEM-ALL D10™. The reactor was purged withnitrogen. 2,480 grams of a 75/25 w/w (weight/weight) EO/PO (ethyleneoxide/propylene oxide) mixture was fed at 100° C. Of the 2,823 grams inthe reactor, 2,230 grams was removed. To the 593 grams remaining in thereactor, 2,950 grams of the mixed oxide was fed at 100° C. Of the 3,543grams in the reactor, 2,985 grams was removed (the product is referredhereinafter as Example 6 Run 2). To the 558 grams remaining in thereactor, 2790 grams of mixed oxide was fed at 100° C. The contents ofthe reactor were drained, (the product is referred hereinafter asExample 6 Run 3). The polymer was so viscous that an accurate massbalance was not possible.

EXAMPLE 7 Preparation of a High Molecular Weight Triol Capped with aPolyethylene Oxide Chain

The final polyether polyol reaction product. of Example 6 Run 2 wasstripped at 90° C. to remove volatiles. A polyether polyol was made byinitiating a reaction (500 g) of the product of Example 6 Run 2dissolved in toluene (600 g). 2485 grams of EO were added at 100° C. tomake an EO capped polyol. The percent hydroxyl of the polyols of Example6 Run 2, Example 6 Run 3 and Example 7 polyether polyols were determinedand the results are compiled in Table 1.

TABLE 1 CALCULATED* BASICITY POLYOL % HYDROXYL MOL. WT. mg KOH/g Example6 Run 2 0.4972 10,258 n.d. Example 6 Run 3 0.1634 31,212 0.015 Example 70.1813 28,130 0.008 *Calculated from the percent hydroxyl corrected forbasicity.

The viscosity of water solutions of several polyols were determined inCannon-Fensky tubes in a thermostatted bath. The results are compiled inTable 2.

TABLE 2 40° C. Viscosity (cS) of Water Solutions Percent of Polyol inExample 6 Example 6 PG Water Run 2 Run 3 Example 7 6000** 10% 4.6 17.615.0 2.3 Solution 20% 11.7 123.7 96.6 7.1 Solution 30% 31 675 1484.718.6 Solution 50% 180 7973 n.d. 107 Solution **Comparison PG6000 isn-butanol initiated 50/50 EO/PO based polyol with a MW of about 5,600.

Several polyols were used to formulate an ISO VG 46 Fluid. The polyolconcentrations in water to achieve an ISO VG 46 fluid are compiled inTable 3.

TABLE 3 Polyglycol Concentration, % Example 6 Run 3 15.0 Example 6 Run 234.9 Synalox 25D700 43 Synalox 25-300B 49 Synalox 25-220B 53 TerraloxHP400 64 Terralox HP670 71 Terralox HP4800 73 PEO 200,000 4 PEO 100,0009 AQUAZOL 500 10 AQUAZOL 200 15 CARBOWAX 20M 19 UCON 75H380,000 23 UCON75H90,000 28 PG 6000 40

Synalox 25D700™ is dipropylene glycol initiated polyol having apolyether chain comprising 65/35 w/w/ EO/PO and having a molecularweight of 5500 MW, available from The Dow Chemical Company.

Synalox 25-300BT™ is dipropylene glycol n-butylether initiated polyolhaving a polyether chain comprising 75/25 w/w EO/PO and having amolecular weight of 3450 MW available from The Dow Chemical Company.

Synalox 25-220B™ is dipropylene glycol n-butylether initiated polyolhaving a polyether chain comprising 75/25 w/w EO/PO and having amolecular weight of 3100 available from The Dow Chemical Company.

Terralox HP400™ is sorbitol initiated ethylene oxide polyol having onaverage 18 moles of ethylene available from The Dow Chemical Company.

Terralox HP670™ is 31/69 w/w glycerin/sucrose initiated propylene oxidepolyol having a molecular weight of 500 MW available from The DowChemical Company.

Terralox HP4800™ is 5/95 w/w glycerin/sucrose initiated propylene oxidepolyol having molecular weight of 1000 available from The Dow ChemicalCompany.

PEO 200,000™ is polyethylene oxide having a molecular weight ofapproximately 200,000 available from Aldrich Chemical.

PEO 100,000™ is polyethylene oxide having a molecular weight ofapproximately 100,000 available from Aldrich Chemical.

CARBOWAX 20M™ is a polyethylene oxide having a molecular weight of about20,000 available from Union Carbide.

AQUAZOL 500™ is a poly(2-ethyl-2-oxazoline) available from PolymerLaboratories having a molecular weight of 500,000.

AQUAZOL 200™ is a poly(2-ethyl-2-oxazoline) available form PolymerLaboratories having a molecular weight of 200,000.

UCON 75H 380,000™ is a polyethylene oxide containing 75/25 EO/POavailable from Union Carbide.

UCON 75H 90,000™ is a polyethylene oxide containing 75/25 EO/PO having amolecular weight of 15,000 available from Union Carbide.

PG 6000TM is a n-butanol initiated 50/50 PO/EO polyol having a molecularweight of about 5600 available from Dow Chemical.

The effect of temperature on the solution viscosity of the polyol of Run3 of Example 6 is illustrated in Table 4.

TABLE 4 Temperature, ° C. Viscosity, cS 25 70 37. 8 50.6 40 48.1

The data in Table 4 demonstrates that polyether polyols of the inventiondemonstrate good ability to maintain viscosity with increasingtemperature.

The polyol of Example 6 Run 3 separated near 50° C. (75/25 EO/PO).

The 100,000 and 200,000 polyethylene oxide polyols heated to 90° C.without any separation of the polymer from the water, the heating wasstopped due to boiling.

The effect of pH on the solution viscosity of the polyol of Example 6Run 3 was determined. After vacuum stripping the polyol of Example 6 Run3 gave a neutral pH. HCl was used to acidify and KOH was added to basifythe polyol. The viscosity of the polyols was examined at 3 pH levels.The results are compiled in Table 5.

TABLE 5 Viscosity, Viscosity, cS @ 40° C. cS @ 40° C. pH Ex. 6 Run 3AQUAZOL 500 Concentration 15% 10% 2.5 45.7 57 7.3 46.5 57 11.9 44 49

Table 5 shows that changes in pH do not affect the viscosity of thepolyether polyols as much as it affects the viscosoty ofpoly(2-ethyl-2-oxazoline).

EXAMPLE 8

Experiments were performed to evaluate the use of solid calcium catalystprepared by the method of U.S. Pat. No. 4,329,047 with catalysts madeaccording to this invention.

TABLE 6 Catalyst Composition Comparative Components Example 8 ExampleCalcium Naphthanate 0 35 Calcium 50 0 Isooctoanate Mineral Spirits 0 60Mineral Spirits 50 0 2-Ethoxyethanol 0 5 Calcium Conc., % 10 4 *Bothcatalyst obtained from OMG Americas, Inc.

The catalyst of Example 8 contains 50 weight percent calciumisooctoanate, with synthetic isooctoanoic acid of high purity, and 50weight percent mineral spirits. The catalyst of Example 8 contains 10weight percent calcium and does not contain any glycol ethers.

The catalyst of the Comparative Example contains 35 weight percentcalcium naphthenate, 60 weight percent mineral spirits and 5 weightpercent 2-ethoxyethanol, a glycol ether. It also contains 4 weightpercent calcium. It is representative of the catalyst used in example 1of Yates U.S. Pat. No. 4,329,047 and prepared according to the teachingsof the patent.

Preparation of Solid Calcium Naphthanate Catalyst Comparative Example

Acetone, 2928.6 grams was added to a 4 L, stirred beaker. The catalystof the Comparative Example as described in Table 6, 207.79 grams wasadded slowly to prevent agglomeration. The white percipitate was allowedto settle for 1 hour. The acetone was decanted and the residualvolatiles were removed at room temperature with vacuum. 116.98 grams ofa thick semi-solid product was recovered.

Preparation of Polyglycol with Solid Calcium Naphthanate Catalyst

Polyglycol P425, 425 molecular weight propylene oxide diol, 98.69 gramswas mixed with 15.69 of the solid Catalyst of the Comparative Exampleprepared as described above. The solid catalyst was not soluble in thepropylene oxide diol. The mixture was added to a dry, 2 gallon, steamheated, stirred, pressure reactor. The reactor was nitrogen purged toremove oxygen. Propylene oxide, 5,740 grams was added over 5 days at atemperature of 120° C. Almost no reaction was observed for the first 2days.

Preparation of Polyglycol with Liquid Calcium Isooctoanate Catalyst,Example 8

Polyglycol P425, 344.1 grams was added to a dry, 5 gallon, steam heated,stirred, pressure reactor. Catalyst of Example 8, 110.1 grams was addedto the reactor. The reactor was nitrogen purged to remove oxygen.Propylene oxide, 5,740 grams was added over 20 hours at a temperature of120° C. An initial time of slow oxide feed rate for two hours wasobserved.

TABLE 7 Production Data Ex. 8 Ex. 8 Comp Ex. Comp. Ex Run Number Run 1Run 2 Run 1 Run 2 Catalyst liquid liquid solid solid Physical State AcidIsoocto- Isoocto- Isoocto- Naphtha- anate anate anate nate InitiatorP425 P425 P425 P425 Initiator 342.2 341.1 278 98.69 (g) Catalyst 111.3110.1 50.6 15.69 (g) Reaction 120° C. 120° C. 120° C. 120° C.Temperature Feed Times* t.b.d. 20 hrs t.b.d. 120 hrs PO (g) 19,86519,805 16,155 5,740 total wt. = 20,319 20,256 16,484 5,854 Unit RatiosInitiator 1.68 1.68 1.69 1.69 Catalyst 0.55 0.54 0.31 0.27 PO 97.7797.77 98.01 98.05 *Actual oxide feed times not including digest and waittimes

Example 8 Runs 1 and 2 and Comparative Example Run 1 were performed in a5 gallon reactor. Comparative Example Run 2 was performed in a 2 gallonreactor. The reaction temperature was the same for all of the runs. Theunit ratios of active catalyst, initiator and propylene oxide is thesame for all of the runs. The feed times for the solid catalyst runswere longer than for the liquid catalyst runs. The initial period ofslow oxide addition was also longer for the solid catalyst runs. Thesolid catalyst of the Comparative Example runs was insoluble in thepolyglycol P425 initiator.

TABLE 8 Properties Of Polyether Polyols Analytical Ex. 8 Ex. 8 Comp. Ex.Comp. Ex. Example Run 1 Run 2 Run 1 Run 2 % OH meas. 0.2817 0.25910.3088 0.44 Unsatura- 0.016 0.003 0.014 0.033 tion Basicity 0.02800.0205 0.0145 0.0136 % OH cor.⁽¹⁾ 0.2341 0.2243 0.3634 0.4169 Calc.MW⁽²⁾ 14,524 15,158 9,357 8,156 Unsat. cor⁽³⁾ 0.016 0.009 0.03 0.03 100F Vis  5,906  7,518 8,163 3,283 SEC Mn 11,342 11,738 10,544  8,394Polydisper- 1.073 1.046 1.077 1.204 sity ⁽¹⁾% OH corrected for basicity⁽²⁾Molecular weight calculated for the % OH corrected assumingfunctionality is 2. ⁽³⁾Unsaturation, meq/g, corrected for basicity

The polyether polyols made with the solid catalyst, (ComparativeExamples), were lower in molecular weight determined by a wet chemicalmethod and higher in unsaturation than the polyether polyols made withthe liquid catalyst, Catalyst of the invention. The number averagemolecular weight (Mn) determined by size exclusion chromatography of thepolyether polyols made with the solid catalyst were lower than thepolyether polyols made with the liquid catalyst. The polydispersity ofthe polyether polyols made with the solid calcium naphthanate catalystwas much higher than the polyether polyols made with the liquid calciumisooctoanate catalyst. The polyether polyols of Example 8 Run 2 andComparative Example were tested by size exclusion chromatography theresults are illustrated in FIG. 1.

The polyether polyol made with the solid calcium naphthanate catalyst,Comparative Example Run 2, contained more low molecular weight speciesthan Example 8 Run 2 made with the liquid calcium isooctoanate catalyst.This is shown in FIG. 1. Comparative Example Run 2, polyether polycolmade with the solid calcium naphthanate catalyst contained 22 weightpercent of species with molecular weights below 10,000 Dalton. Incomparison, Example 8 Run 2 made with the liquid calcium isooctoanatecatalyst had only about 10 percent by weight of species below 10,000Dalton. This is the cause of the low molecular weight determination, thehigh polydispersity and the low viscosity of the polyether polyol ofComparative Example Run 2. The low molecular weight species adverselyaffects the elongation properties of an elastomer made with thispolyether polyol. The polyether polyol made with solid calciumisooctoanate (Comparative Example Run 1) exhibited the same deficienciesas the solid calcium naphthanate prepared polyether polyol but to alesser degree.

The conclusion is that using a solid catalyst in the production of highmolecular weight polyether polyols has several disadvantages: solidcatalysts are difficult to handle in manufacturing plants; solidcatalysts have a longer initial time of slow oxide feed compared toliquid catalysts; solid catalysts have longer feed times than liquidcatalysts; solid catalysts make a polyether polyol with a higherpolydispersity than liquid catalysts, especially the calcium naphthanatecatalyst. Solid catalysts make more lower molecular weight species thanliquid catalysts, especially the calcium naphthanate catalyst.

What is claimed is:
 1. A polyurethane prepolymer prepared by contacting a polyether polyol prepared by the reaction of one or more compounds having one or more active hydrogen compounds with one or more alkylene oxides in the presence of a catalyst consisting of calcium having counterions of carbonate and a C₁₋₆ alkanoate in a solvent which does not contain active hydrogen atoms wherein the polyol prepared has an equivalent weight of from about 1,000 to about 20,000, a polydispersity of 1.30 or less and a residual catalyst level of from about 200 to about 1,000 ppm with one or more polyisocanates under conditions that a polyurethane prepolymer is prepared.
 2. An adhesive composition comprising the polyurethane prepolymer of claim
 1. 3. A polyurethane prepolymer according to claim 1 wherein the polyol corresponds to the formula: R¹—((CH(R²)CH(R²)O)_(m)—H)_(p) wherein: R¹ is the residue of a compound having from about 1 to about 8 active hydrogen atoms or oxygen; R² is independently in each occurrence a hydrogen or a C₁₋₆ saturated or unsaturated hydrocarbon chain; m is independently in each occurrence a number such that the equivalent weight of the polyol is from about 1,000 to about 20,000; and p is independently in each occurrence from about 1 to
 8. 4. A polyurethane prepolymer according to claim 3 wherein: R¹ is independently in each occurrence a C₁₋₈ alkyl or cycloalkyl moiety or oxygen; R² is independently in each occurrence hydrogen, methyl or ethyl; and p independently in each occurrence 4 or less.
 5. A polyurethane prepolymer according to claim 4 wherein: R² is independently in each occurrence hydrogen or methyl; and p is independently in each occurrence 3 or less.
 6. A polyurethane prepolymer according to claim 5 wherein the residual catalyst is a calcium salt and is present in an amount of from about 200 to about 1000 ppm and the polyol has a polydispersity of 1.20 or less and an unsaturation level of 0.04 meq/g or less.
 7. A polyurethane prepolymer according to claim 5 wherein the polyol has a molecular weight of about 2,000 to about 20,000.
 8. An adhesive composition according to claim 2 wherein the polyol corresponds to the formula: R¹—((CH(R²)CH(R²)O)_(m)—H)_(p) wherein: R¹ is the residue of a compound having from about 1 to about 8 active hydrogen atoms or oxygen; R² is independently in each occurrence a hydrogen or a C₁₋₆ saturated or unsaturated hydrocarbon chain; m is independently in each occurrence a number such that the equivalent weight of the polyol is from about 1,000 to about 20,000; and p is independently in each occurrence from about 1 to
 8. 9. An adhesive composition according to claim 8 wherein R¹ is independently in each occurrence a C₁₋₈ alkyl or cycloalkyl moiety or oxygen; R² is independently in each occurrence hydrogen, methyl or ethyl; and p independently in each occurrence 4 or less.
 10. An adhesive composition according to claim 9 wherein R² is independently in each occurrence hydrogen or methyl; and p is independently in each occurrence 3 or less.
 11. A composition useful in preparing an elastomer which comprises a polyurethane prepolymer according to claim 1 and a cross-linking agent.
 12. A composition according to claim 10 wherein the cross-linking agent is present in an amount of from about 1 percent to about 30 percent by weight based on the weight of the elastomer formulation.
 13. An elastomer comprising the reaction product of a polyurethane prepolymer according to claim 1 and a cross-linking agent.
 14. An elastomer according to claim 11 wherein the cross-linking agent is present in an amount of about 1 to about 30 percent by weight based on the weight of the total formulation.
 15. A process for preparing an elastomer which comprises contacting a polyurethane prepolymer according to claim 1 with a cross-linking agent in the presence of a polyurethane catalyst at a temperature of about 15 to about 100° C., to form a reaction product and thereafter exposing to reaction product to a temperature of at least about 80° C. for at least about 1 hour.
 16. A polyurethane prepolymer prepared by contacting a polyether polyol prepared by the reaction of one of more compounds having one or more active hydrogen compounds with one or more alkylene oxides in the presence of a catalyst consisting of calcium having counterions of carbonate and a C₆₋₁₀ alkanoate in a solvent which does not contain active hydrogen atoms wherein the polyol prepared has an equivalent weight of from about 1,000 to about 20,000, a polydispersity of 1.30 or less and a residual catalyst level of from more than 0 to about 1,000 ppm with one or more polyisocyanates under conditions that a polyurethane prepolymer is prepared.
 17. An adhesive composition comprising the polyurethane prepolymer of claim
 16. 18. A process for the preparation of a polyurethane prepolymer wherein a polyol prepared by the reaction of one or more compounds having one or more active hydrogen compounds with one or more alkylene oxides in the presence of a catalyst consisting of calcium having counterions of carbonate and a C₆₋₁₀ alkanoate in a solvent which does not contain active hydrogen atoms wherein the polyol prepared has an equivalent weight of from about 1,000 to about 20,000, a polydispersity of 1.30 or less and a residual catalyst level of from about 0 to about 1,000 ppmis contacted with a polyisocyanate/optionally in the presence of a polyurethane catalyst.
 19. The process of claim 18 wherein the polyol and polyisocyanate are contacted at a temperature of 25° C. to about 150° C. under an inert atmosphere.
 20. The process of claim 19 wherein no polyurethane catalyst is added. 